EP1691604A2 - Inhibiteurs de corrosion pour preparations pesticides aqueuses - Google Patents

Inhibiteurs de corrosion pour preparations pesticides aqueuses

Info

Publication number
EP1691604A2
EP1691604A2 EP04811634A EP04811634A EP1691604A2 EP 1691604 A2 EP1691604 A2 EP 1691604A2 EP 04811634 A EP04811634 A EP 04811634A EP 04811634 A EP04811634 A EP 04811634A EP 1691604 A2 EP1691604 A2 EP 1691604A2
Authority
EP
European Patent Office
Prior art keywords
pesticide
concentrate
corrosion
salt
formulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04811634A
Other languages
German (de)
English (en)
Other versions
EP1691604A4 (fr
EP1691604B1 (fr
Inventor
Michael Syngenta Crop Protection Inc. HOPKINSON
Giulia Syngenta Crop Protection Inc. CAPUZZI
Sarah Syngenta Crop Protection Inc. CUSH
Carolyn Syngenta Crop Protection Inc. MOORE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Syngenta Participations AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Publication of EP1691604A2 publication Critical patent/EP1691604A2/fr
Publication of EP1691604A4 publication Critical patent/EP1691604A4/fr
Application granted granted Critical
Publication of EP1691604B1 publication Critical patent/EP1691604B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides

Definitions

  • the present invention relates to pesticidal concentrates comprising at least one pesticide and an ionic nitrate salt.
  • the present invention also relates to pesticide compositions prepared from these concentrates and to the use of said compositions for controlling pests.
  • Aqueous-based pesticide formulations are increasingly popular due to their improved profile for mammalian toxicity and ecological effects, as well as reduced costs, compared to formulations utilizing an organic solvent as diluent.
  • introduction of even a small amount of water into a pesticide composition increases the potential for corrosion of. metal surfaces of equipment used in manufacturing, storage, transportation or packaging of the product. These corrosion characteristics may result in increased equipment maintenance costs or equipment failure.
  • the use of additives to reduce corrosion in pesticide compositions is known in the art. However, the additives and applications disclosed are very specific in nature. For example, US 2,788,307 discloses use of Na 2 S 2 O 3 to reduce tinplate corrosion in contact with solvent- based lindane or DDT formulations.
  • US 2,630,380 discloses aryloxy polyethylene glycol compounds as inhibitors of corrosion in formulations based on 2,4-dinitro-6-alkylphenols.
  • Use of bis(m-methylphenyl)phosphate to prevent iron corrosion in the presence of S-methyl- N-[(methylcarbamoyl)oxy]thioacetimidate is disclosed in JP 56034562.
  • JP 2000034201 discloses compositions containing silica for preventing corrosion of containers by aqueous aerosols of pyrethroid insecticides.
  • US 5,061,698 discloses compositions based on boric acid with utility as corrosion inhibitors.
  • US 5,032,318 discloses C 13 -C ⁇ 4 alkylamine salts of N- acylsarcosine as corrosion inhibitiors for aerosols in tinplated steel cans.
  • US 5,118,444 discloses use of a specific class of amine oxides to reduce corrosion in aqueous pesticide compositions. The potential for corrosion in aqueous-based formulations is increased when the formulation is acidic in pH. There are a number of important pesticide active ingredients that contain an acid moiety in their structure and an aqueous-based formulation of these products may have an acidic pH. There may be other reasons for the pH of a pesticide formulation to be maintained at an acidic level, such as improved chemical stability for the active ingredient or improved physical stability for the product on storage.
  • nitrate salt additives significantly reduce the corrosion properties of aqueous-based pesticide formulations, even with acidic pH levels and in the presence of a salt.
  • the additives of the present invention may be incorporated in the aqueous pesticide composition during the initial formulation process or may be added at any subsequent stage of storage, transportation or packaging to reduce corrosion.
  • the additives of the present invention have the further advantage of being readily available at relatively low cost.
  • nitrate salts especially ammonium nitrate
  • nitrogen fertilizer carrier liquids involves large quantities per acre.
  • US 5,658,855, US 2003104947, US 2003125211 and WO 02/19823 for use of compositions containing ammonium nitrate as application spray additives for increased herbicide activity.
  • the pesticide compositions that incorporate these additives are very dilute spray mixtures that are typically prepared just prior to use by mixing components directly in the spray equipment.
  • compositions of the present invention have particular utility when the pH of the composition is less than or equal to 6 and/or wherein a salt or metal complex is present, either as the pesticide active ingredient or as a formulation auxiliary.
  • the invention relates to a pesticide concentrate comprising: a) water b) at least one pesticide c) an amount of an ionic nitrate salt additive that is effective in reducing corrosion of metal surfaces d) optionally, other formulation auxiliaries wherein the ratio of component c) to component b) is less than or equal to 0.3 : 1.
  • the invention also relates to pesticide compositions prepared from these concentrates and to the use of said compositions for controlling pests.
  • pesticidal concentrates having reduced corrosion properties can be obtained by incorporating into said concentrate an ionic nitrate salt.
  • the invention relates to a pesticide concentrate comprismg: a) 2-85 % by weight water b) 5-90 % by weight of at least one pesticide c) an ionic nitrate salt additive in an amount effective in reducing corrosion of metal surfaces d) optionally, other formulation auxiliaries. wherein the ratio of component c) to component b) is less than or equal to 0.3:1.
  • the invention also relates to pesticide compositions prepared from these concentrates, to the use of said ionic nitrate salt additives in reducing corrosion of metal surfaces and to the use of said compositions for controlling pests comprising the step of applying to the locus in need of protection an effective amount of the inventive pesticide composition.
  • the compositions of the present invention have particular utility when the pH of the composition is less than or equal to 6 and/or wherein a salt or metal complex is present, either as the pesticide active ingredient or as a formulation auxiliary.
  • Nitrate salts suitable for use as corrosion inhibitor additives in the present invention include ammonium nitrate, alkali metal nitrates and alkaline earth metal nitrates, for example sodium nitrate and calcium nitrate.
  • the additives of the present invention may be incorporated in the pesticide composition during the initial formulation process or may be added at any subsequent stage of storage, transportation or packaging to reduce corrosion.
  • the concentrates of the present invention contain water in a range of 2% to 85% by weight, preferably 5% to 65% by weight.
  • the pesticide concentration ranges from 5% to 90%) by weight, preferably 25% to 75% by weight, with the nitrate salt additive present in an amount effective in reducing corrosion of metal surfaces, typically in a concentration ranging from 0.001% to 10% by weight.
  • the ratio of nitrate salt additive to pesticide concentration is less than or equal to 0.3:1.
  • a preferred embodiment of the invention is a composition comprising ammonium nitrate as the corrosion inhibitor additive.
  • Pesticide active ingredients suitable for the present invention include both water- soluble and water-insoluble compounds.
  • Water-soluble active ingredients include pesticides or plant growth regulators such as acephate, acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, borax, bromacil, bromoxynil, butoxycarboxim, calcium polysulfide, cartap, chloramben, chlormequat, chloroacetic acid, chlorphonium, clofencet, clopyralid, cloxyfonac, copper sulfate, cyanamide, 2,4-D, 2,4-DB, dalapon, daminozide, dicamba, dichlorprop, diclofop, dicrotophos, difenzoquat, dikegulac, diquat, endot
  • pesticides or plant growth regulators such as acephate, acifluorfen, acrolein
  • Preferred water-soluble active ingredients include glyphosate, glufosinate, paraquat, diquat, dicamba, fomesafen, 2,4-D, 2,4-DB and agriculturally acceptable salts thereof.
  • Most preferred water-soluble active ingredients include glyphosate, glufosinate, paraquat and agriculturally acceptable salts and esters thereof.
  • Preferred salts for glyphosate include isopropylammonium, potassium, ammonium and trimethylsulfonium.
  • Water-insoluble active ingredients include pesticides, herbicide antidotes or plant growth regulators such as abamectin, acetochlor, aclonifen, acrinathrin, amitraz, atrazine, azadirachtin, azamethiphos, azinphos-methyl, azocyclotin, azoxystrobin, BAS 670, benalaxyl, benomyl, benoxacor, bensulfuron-methyl, bensultap, benzofenap, 6- benzylaminopurine, bifenox, bifenthrin, bitertanol, bromobutide, bromofenoxim, bromopropylate, bromuconazole, buprofezin, butafenacil, captafol, captan, carbendazim, chinomethionat, chlomethoxyfen, chlorbromuron, chlorfenapyr
  • Preferred water-insoluble active ingredients include mesotrione, and mesotrione metal chelates, atrazine, simazine, terbuthylazine, sulcotrione, metolachlor, s-metolachlor, acetochlor, dimethenamide, abamectin, thiamethoxam, azoxystrobin, metalaxyl, propiconazole, benoxacor, dichlormid, 4-dichloroacetyl-l-oxa4-aza-spiro[4,5]decane, and furilazole.
  • Most preferred water-insoluble active ingredients include mesotrione, and mesotrione metal chelates, atrazine, metolachlor, s-metolachlor, and benoxacor.
  • Preferred mesotrione metal chelates include those wherein the metal is a transition metal selected from the group of copper, cobalt, zinc and nickel.
  • the compositions comprise a metal chelate of mesotrione, preferably a copper or zinc chelate of mesotrione.
  • Formulation auxiliaries that may be present in the form of salts include alkali metal and alkaline earth metal chlorides, such as sodium chloride and calcium chloride.
  • Formulation auxiliaries for the present invention further include, but are not limited to, surface-active agents, thixotropic agents, antifoaming agents, antifreezing agents and preservatives.
  • surfactants will be present in the concentrates of the invention.
  • Suitable surface-active compounds are, depending on the nature of the active ingredient, non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in U.S. Patent No. 6,063,732 column 5, line 1 to column 6, line 2, the contents of which are incorporated herein by reference.
  • surfactants customarily employed in formulation technology which are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, KunststoffNienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for preparation of the herbicidal compositions according to the invention.
  • the amount of surfactant(s) depends on the particular active ingredients selected for the composition and the absolute and relative amounts of these desired.
  • Suitable amounts of stabilizing system components selected from the classes or specific examples provided herein can be determined by routine experimentation, the test being that substantially no phase separation, sedimentation or flocculation is exhibited by the composition following storage at 20-25 °C for a period of 24 hours, or, for preferred embodiments, following a longer period of storage over a broader range of temperatures as indicated above.
  • the total concentration of all surfactants in the composition as a whole is about 1% to about 30% by weight, excluding the weight of counterions, if present.
  • the invention relates also to pesticide compositions obtained by i) diluting the pesticide concentrate of the present invention in a suitable carrier, such as water, such that the final concentration of the pesticide is between about 0.01% and about 10% of active ingredient (a.i.).
  • the invention relates also to a method for the control of pests, said method comprising forming a pesticide composition by i) diluting the pesticide concentrate of the present invention in a suitable carrier, such as water, such that the final concentration of the pesticide is between about 0.01% and about 10% of active ingredient (a.i.) and ii) treating the desired area, such as crop, their seeds or seedlings or the crop area, with said composition.
  • a suitable carrier such as water
  • active ingredient a.i.
  • the invention relates also to the use of an ionic nitrate salt additive in an aqueous pesticide composition for corrosion inhibition.
  • the composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing.
  • composition according to the invention is suitable especially for controlling pests in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, maize and soybeans.
  • “Crops” are to be understood also to include those crops that have been made tolerant to pests and pesticides, including herbicides or classes of herbicides, as a result of conventional methods of breeding or genetic engineering.
  • the components used in the composition of the invention can be applied in a variety of ways known to those skilled in the art, at various concentrations. The rate at which the pesticidal compositions are applied will depend upon the particular type of pest to be controlled, the degree of control required, and the timing and method of application.
  • Crop areas are areas of land on which the cultivated plants are already growing or in which the seeds of those cultivated plants have been sown, and also areas of land on which it is intended to grow those cultivated plants.
  • Other active ingredients such as co-herbicides, fungicides, insecticides, acaricides and nematicides may be present in the emulsifiable concentrate or may be added as a tank-mix partner with the emulsifiable concentrate.
  • Suitable thixotropic additives are compounds that impart a pseudoplastic flow behavior to the formulation, i.e. a high viscosity in the resting state and a low viscosity in the agitated state.
  • Suitable compounds include polysaccharides such as xanthan gum, Kelzan® by Kelco or Rhodopol® 23 by Rhone Poulenc.
  • Suitable antifoams include, for example, silicone emulsions, long-chain alcohols, fatty acids, organofluorine compounds and mixtures of these.
  • test material is prepared according to the following composition:
  • Soprophor BSU surfactant (tristyrylphenol 16 mole ethoxylate) 3.5%
  • control sample (#1) that had no corrosion inhibitor present showed significant corrosion of the 304 stainless steel coupon as indicated by the weight loss of both the welded and flat coupons and visual inspection that showed heavy rust present. Many of the candidate inhibitors actually resulted in increased corrosion while several others showed moderate corrosion inhibition. Two samples (#6, #7) showed weight increases, probably due to plating of copper on the coupons.
  • the ammonium nitrate sample (#18) of the present invention showed a dramatic decrease in corrosion vs. the control as evidenced by a very small weight loss for both coupons and visual inspection that showed no rust or other residue present.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des concentrés pesticides aqueux qui contiennent un additif de sel de nitrate ionique servant d'inhibiteur de corrosion, ainsi que des compositions pesticides préparées à partir de ces concentrés et l'utilisation desdites compositions pour maîtriser des parasites.
EP04811634.7A 2003-12-05 2004-11-19 Inhibiteurs de corrosion pour preparations pesticides aqueuses Active EP1691604B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52755503P 2003-12-05 2003-12-05
PCT/US2004/038945 WO2005060492A2 (fr) 2003-12-05 2004-11-19 Inhibiteurs de corrosion pour preparations pesticides aqueuses

Publications (3)

Publication Number Publication Date
EP1691604A2 true EP1691604A2 (fr) 2006-08-23
EP1691604A4 EP1691604A4 (fr) 2007-02-28
EP1691604B1 EP1691604B1 (fr) 2015-01-07

Family

ID=34710064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04811634.7A Active EP1691604B1 (fr) 2003-12-05 2004-11-19 Inhibiteurs de corrosion pour preparations pesticides aqueuses

Country Status (18)

Country Link
US (1) US8278245B2 (fr)
EP (1) EP1691604B1 (fr)
JP (1) JP4768630B2 (fr)
KR (1) KR101248980B1 (fr)
CN (1) CN100428883C (fr)
AP (1) AP1931A (fr)
AR (1) AR046867A1 (fr)
AU (1) AU2004304890B2 (fr)
BR (1) BRPI0417347B1 (fr)
CA (1) CA2547336C (fr)
EA (1) EA009608B1 (fr)
EC (1) ECSP066601A (fr)
ES (1) ES2531595T3 (fr)
NZ (1) NZ547553A (fr)
TW (1) TWI343788B (fr)
UA (1) UA84895C2 (fr)
WO (1) WO2005060492A2 (fr)
ZA (1) ZA200604487B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0511847B1 (pt) * 2004-06-07 2014-09-16 Syngenta Participations Ag Métodos de reduzir o dano ao material de propagação da planta e órgãos de planta e de melhorar o controle de pragas que habitam o solo direcionado a uma planta por um pesticida
WO2007101620A1 (fr) * 2006-03-06 2007-09-13 Syngenta Participations Ag Granules pesticides stabilisés
JP2009269857A (ja) * 2008-05-08 2009-11-19 Hisao Awano 強化除草剤及びその強化除草剤の使用方法
US20160227782A1 (en) * 2013-09-26 2016-08-11 Borregaard As Pesticide composition and method
CN110770208A (zh) * 2017-06-19 2020-02-07 Upl有限公司 硝磺草酮金属螯合物的多晶型物及其制备方法
CN115584503B (zh) * 2022-10-19 2024-05-17 安徽万磁电子有限公司 降低基材腐蚀的烧结钕铁硼镍铜镍镀层退镀工艺
WO2024105660A1 (fr) * 2022-11-14 2024-05-23 Adama Agan Ltd. Nouveaux systèmes de formulation d'herbicide tricétone

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219348A (en) * 1978-11-16 1980-08-26 Allied Chemical Corporation Storage-stable nitrogen-zinc foliar spray compositions
US5139701A (en) * 1989-05-02 1992-08-18 Betz Laboratories, Inc. Corrosion inhibitors for ferrous metal in aqueous solutions comprising a nonionic surfactant and an anionic oxygen containing group
US5376159A (en) * 1993-09-10 1994-12-27 Nalco Chemical Company Corrosion inhibitor for nitrogen fertilizer solutions
WO1999007918A1 (fr) * 1997-08-11 1999-02-18 Prestone Products Corporation Procede d'inhibition de la corrosion de surfaces metalliques traitees par flux

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265406A (en) * 1979-03-30 1981-05-05 Imperial Chemical Industries Limited Comminution process
GB9108199D0 (en) * 1991-04-17 1991-06-05 Rhone Poulenc Agriculture New compositions of matter
CA2066527C (fr) * 1991-04-22 2000-09-12 Terrence R. Burke Aerosol insecticide avec de l'eau comme solvant
JPH06200241A (ja) * 1992-12-29 1994-07-19 Earth Chem Corp Ltd 水中油滴型エアゾール組成物
ZA96514B (en) * 1995-01-27 1996-08-13 Johnson & Son Inc S C Insecticidally-active composition
US5704961A (en) * 1996-10-17 1998-01-06 Hudson; Alice P. Corrosion inhibitors for liquid fertilizers
US5912207A (en) * 1997-01-31 1999-06-15 Zeneca Limited Stable herbicidal compositions containing metal chelates of herbicidal dione compounds
US20010051591A1 (en) * 2000-04-13 2001-12-13 Ferrett Richard E. Safening crops from the phytotoxic effects of herbicidally active N-phosphonomethyl-glycines
CN1267003C (zh) * 2000-09-08 2006-08-02 辛甄塔合股公司 甲基磺草酮制剂
US6890889B1 (en) * 2000-09-08 2005-05-10 Syngenta Crop Protection, Inc. Mesotrione formulations
GB0114198D0 (en) * 2001-06-11 2001-08-01 Syngenta Ltd Herbicidal composition
GB0213654D0 (en) * 2002-06-13 2002-07-24 Syngenta Ltd Composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219348A (en) * 1978-11-16 1980-08-26 Allied Chemical Corporation Storage-stable nitrogen-zinc foliar spray compositions
US5139701A (en) * 1989-05-02 1992-08-18 Betz Laboratories, Inc. Corrosion inhibitors for ferrous metal in aqueous solutions comprising a nonionic surfactant and an anionic oxygen containing group
US5376159A (en) * 1993-09-10 1994-12-27 Nalco Chemical Company Corrosion inhibitor for nitrogen fertilizer solutions
WO1999007918A1 (fr) * 1997-08-11 1999-02-18 Prestone Products Corporation Procede d'inhibition de la corrosion de surfaces metalliques traitees par flux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2005060492A2 *

Also Published As

Publication number Publication date
AU2004304890A1 (en) 2005-07-07
AR046867A1 (es) 2005-12-28
BRPI0417347A (pt) 2007-03-13
CN1897810A (zh) 2007-01-17
US8278245B2 (en) 2012-10-02
UA84895C2 (ru) 2008-12-10
EA200601097A1 (ru) 2006-12-29
WO2005060492A2 (fr) 2005-07-07
ZA200604487B (en) 2007-04-25
BRPI0417347B1 (pt) 2014-11-25
EA009608B1 (ru) 2008-02-28
JP4768630B2 (ja) 2011-09-07
CA2547336C (fr) 2012-10-30
EP1691604A4 (fr) 2007-02-28
NZ547553A (en) 2009-04-30
WO2005060492A3 (fr) 2005-12-01
AP1931A (en) 2008-12-16
ECSP066601A (es) 2006-10-25
AP2006003644A0 (en) 2006-06-30
EP1691604B1 (fr) 2015-01-07
JP2007513156A (ja) 2007-05-24
CA2547336A1 (fr) 2005-07-07
TW200528029A (en) 2005-09-01
ES2531595T3 (es) 2015-03-17
US20080039329A1 (en) 2008-02-14
KR20060126488A (ko) 2006-12-07
CN100428883C (zh) 2008-10-29
KR101248980B1 (ko) 2013-03-29
TWI343788B (en) 2011-06-21
AU2004304890B2 (en) 2010-11-11

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